Catalyst Design by NH4OH Treatment of USY Zeolite

Hierarchical zeolites are a class of superior catalysts which couples the intrinsic zeolitic properties to enhanced accessibility and intracrystalline mass transport to and from the active sites. The design of hierarchical USY (Ultra‐Stable Y) catalysts is achieved using a sustainable postsynthetic room temperature treatment with mildly alkaline NH₄OH (0.02 m ) solutions. Starting from a commercial dealuminated USY zeolite (Si/Al = 47), a hierarchical material is obtained by selective and tuneable creation of interconnected and accessible small mesopores (2–6 nm). In addition, the treatment immediately yields the NH₄⁺ form without the need for additional ion exchange. After NH₄OH modification, the crystal morphology is retained, whereas the microporosity and relative crystallinity are decreased. The gradual formation of dense amorphous phases throughout the crystal without significant framework atom leaching rationalizes the very high material yields (>90%). The superior catalytic performance of the developed hierarchical zeolites is demonstrated in the acid‐catalyzed isomerization of α‐pinene and the metal‐catalyzed conjugation of safflower oil. Significant improvements in activity and selectivity are attained, as well as a lowered susceptibility to deactivation. The catalytic performance is intimately related to the introduced mesopores, hence enhanced mass transport capacity, and the retained intrinsic zeolitic properties.     

Developing a conductive oxygen barrier for ferroelectric integration

For high-density FeRAM memories, the 1T–1C architecture has been proposed. In this scheme, the ferrocapacitor (FeCAP), a metal\ferroelectric film\metal-like sandwich, is placed directly on top of polysilicon or tungsten plugs contacted to the underlying CMOS technology. Our ferroelectric material of choice, SrBi₂Ta₂O₉ (SBT), requires crystallization anneals ranging from 650 to 800 °C in full oxygen. The bottom electrode (BE) needs to be conductive, as well as an oxygen barrier to protect the underlying plug from oxidation. We have developed a BE stack combination consisting of Pt/IrO₂/Ir/Ti(Al)N. Each layer plays a critical role in the performance of the barrier. Issues such as thermal expansion, stress relaxation, grain growth, and oxidation can be critical in order to have a working bottom electrode. For capacitor formation, the complete stack is etched and covered by SBT. Since all layers are in contact with SBT, it is important to understand how the ferroelectric interacts with both the individual layers and the combined structure. In this paper, we will present our understanding of the chemical reactivity between SBT and the BE stack, which has been successfully engineered to prevent oxidation of the underlying plug.     

Single Cell Bioprinting with Ultrashort Laser Pulses

Tissue engineering requires the precise positioning of mammalian cells and biomaterials on substrate surfaces or in preprocessed scaffolds. Although the development of 2D and 3D bioprinting technologies has made substantial progress in recent years, precise, cell-friendly, easy to use, and fast technologies for selecting and positioning mammalian cells with single cell precision are still in need. A new laser-based bioprinting approach is therefore presented, which allows the selection of individual cells from complex cell mixtures based on morphology or fluorescence and their transfer onto a 2D target substrate or a preprocessed 3D scaffold with single cell precision and high cell viability (93–99% cell survival, depending on cell type and substrate). In addition to precise cell positioning, this approach can also be used for the generation of 3D structures by transferring and depositing multiple hydrogel droplets. By further automating and combining this approach with other 3D printing technologies, such as two-photon stereolithography, it has a high potential of becoming a fast and versatile technology for the 2D and 3D bioprinting of mammalian cells with single cell resolution.     

Error-resilient decoding of context-based adaptive binary arithmetic codes

This paper addresses the problem of error-resilient decoding of bitstreams produced by the CABAC (context-based adaptive binary arithmetic coding) algorithm used in the H.264 video coding standard. The paper describes a maximum a posteriori (MAP) estimation algorithm improving the CABAC decoding performances in the presence of transmission errors. Methods improving the re-synchronization and error detection capabilities of the decoder are then described. A variant of the CABAC algorithm supporting error detection based on a forbidden interval is presented. The performances of the decoding algorithm are first assessed with theoretical sources and by considering different binarization codes. They are compared against those obtained with Exp-Golomb codes and with a transmission chain making use of an error-correcting code. The approach has been integrated in an H.264/MPEG-4 AVC video coder and decoder. The PSNR gains obtained are discussed.     

Mesoporous Silicon‐PLGA Composite Microspheres for the Double Controlled Release of Biomolecules for Orthopedic Tissue Engineering

In this study, poly(dl ‐lactide‐co‐glycolide)/porous silicon (PLGA/pSi) composite microspheres, synthesized by a solid‐in‐oil‐in‐water (S/O/W) emulsion method, are developed for the long‐term controlled delivery of biomolecules for orthopedic tissue engineering applications. Confocal and fluorescent microscopy, together with material analysis, show that each composite microsphere contained multiple pSi particles embedded within the PLGA matrix. The release profiles of fluorescein isothiocyanate (FITC)‐labeled bovine serum albumin (FITC‐BSA), loaded inside the pSi within the PLGA matrix, indicate that both PLGA and pSi contribute to the control of the release rate of the payload. Protein stability studies show that PLGA/pSi composite can protect BSA from degradation during the long term release. We find that during the degradation of the composite material, the presence of the pSi particles neutralizes the acidic pH due to the PLGA degradation by‐products, thus minimizing the risk of inducing inflammatory responses in the exposed cells while stimulating the mineralization in osteogenic growth media. Confocal studies show that the cellular uptake of the composite microspheres is avoided, while the fluorescent payload is detectable intracellularly after 7 days of co‐incubation. In conclusion, the PLGA/pSi composite microspheres offer an additional level of controlled release and could be ideal candidates as drug delivery vehicles for orthopedic tissue engineering applications.     

Highly Ordered Self‐Assembled Architectures of Modified Terpyridines on Highly Ordered Pyrolitic Graphite Imaged by Scanning Tunneling Microscopy

Scanning tunneling microscopy has been used to study the adsorbed phases of functionalized terpyridines at the solid–liquid interface of highly ordered pyrolitic graphite (HOPG). Terpyridines are well‐known for their complexing behavior to transition metal ions, making them widely used ligands in organometallic and supramolecular chemistry. We found that solutions of 2,2′:6′,2″‐terpyridine‐4′‐oxydodecane (tpy‐O‐C12) and 2,2′:6′,2″‐4′‐oxyoctadecane (tpy‐O‐C18) form highly ordered two‐ dimensional (2D) arrays on HOPG in phenyloctane. For both compounds, large, well‐defined lamellar domains have been observed with domain sizes larger than 500 nm. Sequential scans of an area with two grain boundaries indicate that desorption–resorption is taking place along the domain edges. High‐resolution images of the lamella have been obtained, and the 2D packing within the lamella was determined in detail. The terpyridines align in long uniform double rows with their alkyl chains packing in an alternating, zipper‐like fashion. The terpyridines pack with the polar head‐groups head to head, and the observed size and shape of the molecules fit exactly to their modeled geometries.